High bulk density carbonate-zeolite built heavy duty nonionic laundry detergent

ABSTRACT

A free flowing phosphate-free high bulk density particulate heavy duty nonionic laundry detergent is comprised of particles of spray dried base beads containing ion exchanging zeolite and sodium carbonate with which is mixed a particulate water soluble sodium silicate and into which is absorbed a nonionic detergent. The product is made by spray drying an aqueous mixture or slurry of the zeolite and carbonate, mixing with the beads produced a water soluble silicate powder such as hydrous sodium silicate of Na 2  O:SiO 2  ratio of about 1:2 and mixing nonionic detergent in liquid form with the mixture of spray dried base beads and silicate powder and absorbing the nonionic detergent into said mixture.

This is a division of application Ser. No. 384,994 filed June 4, 1982now U.S. Pat. No. 4,406,808, which is a continuation of application Ser.No. 839,781; filed Oct. 6, 1977, now abandoned.

This invention relates to built synthetic organic detergent compositionsuseful for the heavy duty laundering of washable clothing and othertextile items, and to a method for the manufacture thereof. Moreparticularly, it relates to an improved non-phosphate synthetic organicdetergent composition based on nonionic synthetic organic detergent,synthetic zeolite builder, sodium carbonate and hydrous sodium silicate,which is free flowing and of high bulk density and deposits littleresidue on washed materials.

Although synthetic organic detergent compositions have long been basedon mixtures of synthetic organic detergent, usually anionic detergent,such as a linear alkyl benzene sulfonate, and builder salt, usuallypentasodium tripolyphosphate, because of anti-eutrophication laws andgovernmental regulations the phosphate content of heavy duty detergentcompositions has been limited and in some instances it has beenconsidered desirable to produce low phosphate or phosphate-freedetergent compositions. Water insoluble builders, such as bentonite andnatural zeolites had previously been employed in soap and syntheticorganic detergent compositions for their desirable effect in removinghardness ions, such as calcium and magnesium ions, from wash waters.More recently, with the availability of synthetic zeolites of improvedhardness ion-counteracting properties, such zeolites have been includedin detergent products to remove such ions and to improve detergency ofthe synthetic organic (usually anionic) detergent present. Such productsmay be of low phosphate content or free of phosphate and may bechemically inactive and non-nutritive, hence not contributing to algaegrowth and eutrophication of inland waters. Although the detergentcompositions may be advantageous in those respects, it has been notedthat materials washed with them can have objectionable quantities ofresidue deposited on them. This is most objectionable when thelight-colored residue is readily apparent on a dark material.Accordingly, efforts have been made to reduce the depositing of suchresidue while still producing a satisfactory detergent. In U.S. Pat. No.3,985,669 it is reported that less residue is present in such detergentcompositions when the quantity of silicate is maintained low. However,with comparatively large quantities of synthetic zeolite, especiallythat of a type prone to deposit on such substrates, objectionabledeposits can still result. Also, reducing the proportion of silicatepresent may diminish the anti-corrosive effect of such normallydesirable component of synthetic detergent compositions. Accordingly,other ways of preventing such deposits have been the subjects ofresearch projects.

Recently it has been considered desirable by the assignee of the presentinvention to produce free flowing and comparatively high bulk densityparticulate heavy duty laundry detergents so that relatively smallquantities of these can be employed and will effectively clean in normalheavy duty laundering operations. It has been found that a combinationof nonionic detergent, synthetic zeolite, sodium carbonate and sodiumbicarbonate can be made into a free flowing, high bulk density,phosphate-free product. For example, in U.S. patent application Ser. No.747,002, filed Dec. 2, 1976, in which one of the present co-inventors isthe named inventor, a mixed salt, such as Wegscheider's salt, is tumbledwith nonionic detergent and the product is coated with synthetic zeolitepowder. While the products made are useful detergents of desired highbulk density, they may be of somewhat different appearance from that ofconventional detergents normally purchased by the householder andtherefore they might not be as readily accepted in the marketplace.Also, products which are spray dried or are made substantially fromspray dried base beads, which are produced from homogeneous crutchermixes, tend to be more uniform in composition and when materials blendedwith them constitute only minor proportions of the final productgenerally the post-spraying and mixing processes utilized in theirmanufacture do not require as strict control to ensure obtainingproduction of desirably homogeneous and free flowing products, comparedto the method of Ser. No. 747,002, for example. Additionally, mostdetergent manufacturers are equipped with spray drying facilities andcontinuation of the use of such is often economically desirable. Thepresent methods allow production of a free flowing, high bulk density,phosphate-free (or low phosphate) heavy duty laundry detergent ofnon-sifting characteristics, good washing properties, low residuedeposition characteristics and attractive appearance to be readilycarried out by methods utilizing for a substantial part equipmentalready on hand and with which operators are familiar.

In accordance with the present invention a method of manufacturing afree flowing, phosphate-free, particulate heavy duty laundry detergentof bulk density greater than 0.6 g./ml. comprises spray drying anaqueous mixture of ion exchanging zeolite, sodium carbonate and water toa moisture content in the range of about 2 to 16% so that the proportionof zeolite to sodium carbonate in the spray dried beads produced is inthe range of 1:0.1-1.5 and mixing with said beads from 0.1 to 0.3 partof hydrous sodium silicate in particulate form and 0.2 to 1.0 part ofnonionic detergent in liquid form per part of zeolite so that suchdetergent is absorbed into the beads. The invention is also in theproduct resulting and other such products which comprise beads ofzeolite and sodium carbonate in the proportion of 1:0.1-1.5, havingmixed with them from 0.1 to 0.3 part of hydrous sodium silicate inparticulate form and 0.2 to 1.0 part of nonionic detergent per part ofzeolite, which nonionic detergent is absorbed into the spray dried beadsand may hold the hydrous silicate in or on the beads. Proportions givenare on anhydrous bases.

Nonionic detergents are listed at length in McCutcheon's Detergents andEmulsifiers, 1973 Annual and in Surface Active Agents, Vol. II, bySchwartz, Perry and Berch (Interscience Publishers, 1958), thedescriptions of both of which are hereby incorporated by reference. Suchdetergents may be liquid, pasty or waxy solids at room temperature (20°C.) and are usually either sufficiently water soluble to dissolvepromptly in water or will quickly melt at the temperature of the washwater, as when that temperature is about 30° or 40° C. While thenonionic detergent employed will normally be one which is either liquidor pasty at room temperature, often preference will be given to normallyliquid products because these readily penetrate into the interiors ofthe base particles, surprisingly leaving little or no material at thesurfaces thereof, thus avoiding any tackiness due to presence of thenonionic detergent at the particle surfaces. The use of the normallyliquid nonionic detergents allows room temperature application of thenonionic material to the base particles and avoids problems encountereddue to any premature solidification of the nonionic or due to thepresence of a pasty material near the surfaces thereof, which can be theresult of undesired quick cooling of such nonionic detergent before ithas satisfactorily penetrated into the interior of the base particle.Thus, although it would have been expected that one would prefer toemploy a solid ionic detergent or at least one which is normally pastyor semi-solid because it would be considered that such would be lessliable to make a tacky product of poor flow properties andsusceptibility toward lumping or setting on storage than liquid nonionicdetergents, this is not the case. If the base beads are kept warm enoughand the nonionic detergent is applied in liquid state, as may beeffected when normally solid or pasty nonionic detergent is heatedsufficiently, the product resulting, providing that penetration into thebase bead interior is sufficient, will be as good as the preferredliquid nonionic detergent-base bead compositions with respect to theflow and non-lumping properties but even in such case the liquidnonionic detergent is more amenable to being dispersed readily inaqueous media and therefore is more quickly effective in wash water.Generally, if a normally pasty, semi-solid or solid nonionic detergentis employed, when it is applied to the base beads it will be in theliquid state and usually will be at a temperature below 50° or 60° C.,always below 70° C. and preferably below 45° C. For example, when anormally solid nonionic detergent such as Alfonic 1618-65 is employed,it will be heated so as to be a liquid upon application but when Neodol25-6.5 or 25-7 is used heating will be unnecessary, providing that roomtemperature application, such as at 25° C., is effected.

Typical useful nonionic detergents are the poly- (lower alkenoxy)derivatives that are usually prepared by the condensation of lower (2 to4 carbon atoms) alkylene oxide, e.g., ethylene oxide, propylene oxide(with enough ethylene oxide to make a water soluble product), with acompound having a hydrophobic hydrocarbon chain and containing one ormore active hydrogen atoms, such as higher alkyl phenols, higher fattyacids, higher fatty mercaptans, higher fatty amines and higher fattypolyols and alcohols, e.g., fatty alcohols having 8 to 20 or 10 or 12 to18 carbon atoms in an alkyl chain and alkoxylated with an average ofabout 3 to 30, preferably 5 to 20 and more preferably 5 to 12 loweralkylene oxide, e.g., ethylene oxide, units. Preferred nonionicdetergents are those represented by the formula

    RO(C.sub.2 H.sub.4 O).sub.n H

wherein R is the residue of a linear saturated primary or secondaryalcohol (an alkyl) of 10 to 18 carbon atoms and n is an integer from 5to 20 or 5 to 12. The preferred nonionic detergents may be referred toas higher fatty alcohol polyoxyethylene ethanols (the terminal ethanolicpart of these ethers is included in the number of oxyethylene groupscounted in the mol of the nonionic). Typical commercial nonionic surfaceactive agents suitable for use in the invention include Neodol®23-6.5,an ethoxylation product with an average of about 6.5 mols of ethyleneoxide per mol of a 12 to 13 carbon atom chain fatty alcohol, Neodol25-7, a 12 to 15 carbon atom chain fatty alcohol ethoxylated with anaverage of 7 of the ethylene oxide units, Neodol 45-11, which is anethoxylation product (having an average of about 11 ethylene oxideunits) of a 14 to 15 carbon atom (average) chain fatty alcohol (all madeby Shell Chemical Company) and Alfonic®1618-65, which is a 16 to 18carbon alkanol ethoxylated with an average of 10 to 11 ethylene oxideunits (Continental Oil Company). Also useful are the Igepals® of GAFCo., Inc. In the above description higher, as applied to higher alkyl,higher fatty, etc., means that 8 to 20, preferably from 10 or 12 to 18carbon atoms are present.

The zeolites utilized in the present invention include the crystalline,amorphous and mixed crystalline-amorphous zeolites of natural orsynthetic origin or mixtures thereof that will be of satisfactorilyquick and sufficiently effective hardness ion counteracting activity.Preferably, such materials are able to react sufficiently rapidly with ahardness cation, such as one of calcium, magnesium, iron and the like,to soften the wash water before adverse reactions of such hardness ionswith fibers of the laundry, any soils thereon and any constituents ofthe synthetic organic detergent compositions made according to thepresent invention, or any combination thereof. The useful range ofcalcium ion exchange capacities is from about 200 milligram equivalentsof calcium carbonate hardness per gram of aluminosilicate to 400 or moreof such milligram equivalents (on an anhydrous zeolite basis), per gram.Preferably such range is about 250 to 350 milligram equivalents pergram.

The water insoluble crystalline aluminosilicates used are oftencharacterized by having a network of substantially uniformly sized poresin the range of about 3 to 10 Angstroms, often being about 4 Å(nominal), such size being uniquely determined by the unit structure ofthe particular type of zeolite crystal. Of course, zeolites containingtwo or more such networks of different pore sizes can also besatisfactorily employed, as can be mixtures of such crystallinematerials with each other and with amorphous materials.

The zeolite should be a univalent cation-exchanging zeolite, i.e., itshould be an aluminosilicate of a univalent cation, such as sodium,potassium, lithium (when practicable) or other alkali metal or,ammonium. Preferably the univalent cation of the zeolite molecular sieveis an alkali metal cation, especially sodium or potassium, and mostpreferably is sodium, but various other cations are also useful.

Crystalline types of zeolites utilizable as molecular sieves in theinvention, at least in part, include zeolites of the following crystalstructure groups: A, X, Y, L, mordenite, and erionite, of which types Aand X are preferred. Mixtures of such molecular sieve zeolites can alsobe useful, especially when type A zeolite is present. These crystallinetypes of zeolites are well known in the art and are more particularlydescribed in the text Zeolite Molecular Sieves, by Donald W. Breck,published in 1974 by John Wiley & Sons. Typical commercially availablezeolites of the aforementioned structural types are listed in Table 9.6at pages 747-749 of the Breck text, which table is incorporated hereinby reference.

Preferably the zeolite used in the invention is synthetic and it is mostpreferable that it be of type A or similar structure, particularlydescribed at page 133 of the aforementioned text. Good results have beenobtained when a Type 4 A molecular sieve zeolite is employed, whereinthe univalent cation of the zeolite is sodium and the pore size of thezeolite is about 4 Angstroms. Such zeolite molecular sieves aredescribed in U.S. Pat. No. 2,882,243, which refers to them as Zeolite A.

Molecular sieve zeolites can be prepared in either a dehydrated orcalcined form which contains from about 0 or about 1.5% to about 3% ofmoisture or in a hydrated or water loaded form which contains additionalbound water in an amount from about 4 up to about 36% of the zeolitetotal weight, depending on the type of zeolite used. Thewater-containing or hydrate form of the molecular sieve zeolite ispreferred in the practice of this invention. The manufacture of suchhydrated crystals is well known in the art. For example, in thepreparation of Zeolite A, referred to above, the hydrated zeolitecrystals that are formed in the crystallization medium (such as ahydrous amorphous sodium aluminosilicate gel) are used without the hightemperature dehydration (calcining to 3% or less water content) that isnormally practiced in preparing such crystals for use as catalysts,e.g., cracking catalysts. The crystalline zeolite, in either completelyhydrated or partially hydrated form, can be recovered by filtering offthe crystals from the crystallization medium and drying them in air atambient or other suitable temperature so that their water contents areas desired, usually being in the range of about 5 to 20% moisture,preferably 15 to 22%. However, because at least partial hydration maysometimes be effected during manufacture of the compositions of thepresent invention, the moisture content of the molecular sieve zeolitebeing employed may sometimes be as low as 0 percent at the start of theprocess of manufacturing the present detergent compositions.

Preferably the zeolite to be used will be initially in a finely dividedstate, with the ultimate particle diameters being below 15 microns,e.g., 0.001 to 15 microns, preferably being from 0.01 to 10 microns andespecially preferably of 0.01 to 8 microns in mean particle size, e.g.,4 to 8 microns, if crystalline and 0.01 to 0.1 micron, e.g., 0.01 to0.05 micron, if amorphous.

Although the crystalline synthetic zeolites are more common and betterknown, amorphous zeolites may be employed instead and are often superiorto the crystalline materials in various important properties, as will bedescribed, as may be mixed crystalline-amorphous materials and mixturesof the various types of zeolites described. The particle sizes are poresizes of such materials will usually be like those previously describedbut variations from the described ranges may be made, providing that thematerials function satisfactorily as builders in the presentcompositions and do not objectionably overwhiten dyed materials withwhich they are treated in aqueous media. Various suitable crystallinemolecular sieve zeolites are described in four U.S. patent applicationsof Bao-Ding Cheng, Serial Nos. 467,688, filed May 7, 1974; 503,734,filed Sept. 6, 1974; and 640,793 and 640,794, filed Dec. 15, 1975, allof which are hereby incorporated by reference for such descriptions andfor descriptions therein of other materials within this invention. Otheruseful such molecular sieve zeolites are illustrated in GermanOffenlegungsschriften Nos. 2,412,837 and 2,412,839 both of which areincorporated herein by reference. U.S. Pat. No. 3,985,669 and U.S.patent application Ser. No. 747,002, previously mentioned, areincorporated by reference, too, for their descriptions of zeolites andother components of the present compositions and other relevantdisclosures. A preferred ion exchange zeolite is the amorphous zeoliteof Belgian Pat. No. 835,351 of the formula

    M.sub.2 O.Al.sub.2 O.sub.3.(SiO.sub.2).sub.z.wH.sub.2 O

wherein M is a monovalent cation, preferably an alkali metal, z is from1.5 or 2.0 to 3.8 or 4 (2 is sometimes preferable) and w is from 2.5 to6, especially when M is sodium. Such patent and applications are alsoincorporated herein by reference to avoid the necessity for lengthyrecitations of such materials, methods for their manufacture and uses,etc.

The formula given above may be varied to

    (Na.sub.2 O).sub.x.(Al.sub.2 O.sub.3).sub.y.(SiO.sub.2).sub.z.wH.sub.2 O

and usually, when x is 1, y will be from 0.8 to 1.2, z will be from 1.5to 5 and w will be 0 to 9, such limits preferably being 0.9 to 1.1, 2.0and 3.8 and 2.5 to 6 or 3.0 to 4.5 thereabout. The chemical orstructural formula will preferably be the following or approximately ofthat formula:

    (Na.sub.2 O).sub.6 (Al.sub.2 O.sub.3).sub.6 (SiO.sub.2).sub.12.27H.sub.2 O

but the mols of water present may be 15 to 27, e.g., 20 or 24 to 27.Note that in such chemical formula the x:y:z:w ratio is 1:1:2:4.5.

The alkali metal carbonate employed will desirably be of particle sizeswithin the No. 20 to 200 range U.S. Sieve Series (preferably 100 to200), but various other sizes of particles, up to about 8 mesh and asfine as 325 mesh may be used, providing that they dissolve and/ordisperse readily in the aqueous crutcher mix. Solutions may also beemployed, provided that moisture contents of the crutcher mix resultingare not thereby raised too high. Normally the alkali metal (sodium orpotassium being preferred) carbonate, most preferably as the sodiumsalt, will be essentially anhydrous in preferred embodiments of theinvention but partially hydrated carbonates may also be used. Thepowdered carbonate is readily made into a suitable aqueous slurry withthe zeolite and water, which slurry is easily spray dried to particleswhich readily sorb nonionic detergent, either alone or mixed with asuitable silicate such as a water soluble (hydrous) silicate. It ispreferred that the carbonate employed be essentially pure sodiumcarbonate, usually over 95% pure, without the presence of bicarbonatewhich is in sodium sesquicarbonate, Wegscheider's salt or the commercialproducts which are mixtures of carbonates and bicarbonates, such asSnowlites, I and II (Allied Chemical Corporation).

The water of the crutcher mix and of the final product is preferablydeionized water or water which may be present as the solvent in aqueoussolution or dispersion of one or more of the components of the crutchermix. The water employed, if added, will usually have a hardness contentof less than 150 p.p.m., preferably less than 50 p.p.m. and morepreferably less than 10 p.p.m., calculated as calcium carbonate.Although deionized water is preferable, tap waters low in hardnesscontents may also be employed. The moisture contents of the products arethose which are removable by heating to a temperature of 105° C. forfive minutes.

The water soluble alkali metal silicate which is employed is that whichis usually referred to as a hydrous alkali metal silicate, preferablysodium silicate of Na₂ O:SiO₂ ratio in the range of 1:1.5 to 1:2.5,preferably 1:1.8 to 1:2.4, e.g., 1:2. Although it is possible to addsuch silicate to the aqueous crutcher with the carbonate and the zeolitewhen, in making the present detergent compositions, such procedure isfollowed, objectionable deposits of residues are sometimes noted onwashed fabrics or laundry and because such deposits are to be avoidedand it has been found that they are substantially avoided bypost-addition of hydrous alkali metal silicate, such post-additionmethod is normally utilized. In post-addition the hydrous sodiumsilicate, preferably in particulate or powdered form, usually with theparticle sizes in the 10 to 200 mesh range, e.g., 10 to 150 mesh, willbe admixed with the spray dried base beads of zeolite and carbonatebefore spraying onto tumbling surfaces of such mixture the nonionicdetergent in liquid form for sorption by the spray dried beads and, tosome extent, by the hydrous silicate. Typical hydrous sodium silicatescreen analyses (for Britesils H20 and H24) follow: 55% through No. 10sieve and on No. 48; 40% through 48, on 65; 4% through 65, on 100; and3% through 100 on 150.

In addition to the mentioned components of the final product, inpreferred compositions various adjuvants will also be favored. Forexample, to improve cleaning a proteolytic enzyme or equivalent enzymemay be post-added (normally such are not included in the crutcher mixbecause spray drying has an inactivating effect on such enzymes). Theenzymes that may be employed are generally effective at pH ranges fromabout 4 to 12, preferably about 8 to 11. Although the proteolyticenzymes are subject to some degradation by heat they may be employed inwashing solutions at temperatures up to about 80° C. and are alsoeffective at low temperatures, down to about 10° C. Among theproteolytic enzymes that are useful may be mentioned pepsin, trypsin,chymotrypsin, bromelain, collagenase, keratinase, carboxylase, aminopeptidase, elastase, subtilisin and aspergillopepidases A and B.Preferred enzymes are subtilisin enzymes manufactured and cultivatedfrom special strains of spore-forming bacteria, particularly Bacillussubtilis.

Proteolytic enzymes such as Alcalase, Maxazyme, Protease AP, ProteaseATP 40, Protease ATP 120, Protease L-252 and Protease L-432 are amongthose enzymes derived from strains of spore forming bacilli, such asBacillus subtilis. Different proteolytic enzymes have different degreesof effectiveness in aiding in the removal of stains from textiles andlinen. Particularly preferred as stain removing enzymes are subtilisinenzymes. Metalloproteases which contain divalent ions such as calcium,magnesium or zinc bound to their protein chains are of interest. Themanufacture of proteolytic enzyme concentrates is described in GermanOffenlegenschrift No. 1,800,508 and in Dutch patent application, No.6,815,944.

Instead of or in partial replacement of the proteolytic enzyme, otherenzymes may also be used, usually for specific purposes. Thus, anamylase may be employed, e.g., acterial amylase of the alpha type, suchas is obtained by fermentation of Bacillus subtilis. Among the otherenzymes that may be used are those characterized as hydrolytic,lipolytic, oxidizing, reducing and glycolytic. Such include catalase,lipase, maltase and phosphatase. The mentioned enzymes and classesthereof, while considered to be most useful, are not the only effectiveones in the present products. Virtually any enzymes that contribute toloosening of the bonds by which soils or stains are held to fibrousmaterials may be used in present formulas. Guides to such use may befound in Principles of Biochemistry by White, Handler, Smith and Stetten(1954).

Another preferred component of the present laundry detergents is afluorescent brightener. The fluorescent brighteners are members of awell-known class in the detergent art and usually are reaction productsof cyanuric chloride and the disodium salt of diamino stilbenedisulfonic acid, benzidine sulfone disulfonic acid, amino coumarins,diphenyl pyrazoline derivatives or naphthotriazolyl stilbenes. Suchmaterials are described in the article Optical Brighteners and TheirEvaluations by Per S. Stensby, a reprint of articles published in Soapand Chemical Specialties in April, May, July, August and September,1967, especially at pages 3-5 thereof. Among such brighteners areTinopal 5BM (Geigy), Tinopal RBS, SOF (Ciba), and one known as StilbeneNo. 4, disodium4,4'-bis-(4-anilino-6-morpholine-s-triazine-2-ylamino)-2,2'-stilbenedisulfonate. Of these, Tinopal 5BM is generally preferred.

Various other constituents and adjuvants may be present in the crutchermix or may be post-added, including foam improvers, foam depressants,fungicides, antioxidants, sanitizers, stabilizers, chelating agents,soil suspending agents, soil anti-redeposition agents, colorants(pigments and dyes), bleaches and perfumes. Such materials arewell-known in the art and need not be recited at length here. Withrespect to the making of the crutcher mix it is highly preferred to omitfrom such mix any surface active or detersive materials, which tend toproduce lower bulk density spray dried beads.

The proportions of active materials in the final product should be inthe range of 1:0.1-1.5:0.1-0.3:0.2-1.0 forzeolite:carbonate:silicate:nonionic detergent. Preferably, suchproportions will be 1:0.2-1.0:0.15-0.25:0.3-0.8, respectively.Percentagewise, such constituents plus water are 25 to 70% of syntheticzeolite, 8 to 35% of sodium carbonate, 5 to 15% of hydrous sodiumsilicate, 15 to 25% of nonionic detergent and 2 to 15% of water.Normally 0 to 10% of adjuvants, e.g., 2 to 7% are also present.Preferably such percentages will be 30 to 60% of synthetic zeolite, 8 to30% of sodium carbonate, 7 to 12% of hydrous sodium silicate, 17 to 23%of nonionic detergent and 5 to 12% of water. In a particular preferredformulation there will be present about 45% of zeolite, 13% of sodiumcarbonate, 8.1% of hydrous sodium silicate, 20% of nonionic detergent,2% of fluorescent brightener, 1.5% of proteolytic enzyme, 0.2% ofpigment, 0.3% of perfume and 9.9% of water. The fluorescent brightenercontent of these products will normally be in the range of 0.05 to 3%,preferably 1 to 2.5% and the proteolytic enzyme content, includingnormally present carrier for such enzyme, will be from 0.5 to 3%,preferably 1 to 2%, when present. Various other adjuvants which may alsobe employed will normally not total more than 5% and preferably will beless than 3%, with the percentages of individual components being lessthan 1% and preferably 0.5% or less. Thus, from 0.1 to 0.4% pigment maybe present, as may be 0.1 to 0.4% perfume. If desirable, the percentageof anti-redeposition agent may be as high as 1% but normally thepercentage thereof, if present, will be from 0.5-2.0%.

In the crutcher mix the percentages of components are usually 20 to 60%of zeolite, 5 to 30% of carbonate and 25 to 60% of water, possibly with1 to 5% of adjuvants, too.

The high bulk density particulate heavy duty laundry detergent productof this invention will usually be in free flowing rounded bead form suchas that of other spray dried products, although the bead interior may bevirtually honeycombed. The particle sizes of the beads will normally bein the range of No's. 6 to 160 sieve, preferably No;s. 8 to 100 sieve,with less than 10%, preferably less than 5% and more preferably lessthan 1% of the product being outside such ranges. The bulk density ofthe finished detergent will normally be at least 0.6 g./ml., preferablyat least 0.65 g./ml. and most preferably is in the 0.65 to 0.85 g./ml.range, e.g. 0.71 to 0.83 g./ml. The flow rates of such products areexcellent and usually will be greater than 70% of the rate of freeflowing sand of similar particle size, normally being from 70 to 95%thereof and preferably 75 to 95% thereof. Although the 0.65 to 0.85g./ml. bulk density range is preferred, by changing formulas and spraydrying techniques it can be changed upwardly and downwardly, e.g., to0.5 and 0.9 g./ml.

In the manufacture of the invented laundry detergent it is importantthat a sorptive bead be made for absorption of nonionic detergenttherein. Such sorption should be sufficient so that the nonionicdetergent is passed into the bead interior and therefore does not tendto cause caking of the beads or poor flow properties. While some formsof sodium carbonate have been found to be good sorbents for nonionicdetergents (most are not), products made with the acceptable sorbentalone as the builder, at least in quantities needed to make compositionsof the type which are acceptably detersive tend to have objectionablyhigh pH's. Even so, such products are not as free flowing as those ofthe present invention. For example, Flozan, a sodium carbonate formerlymanufactured by Diamond Shamrock Corp., could absorb 20% of nonionicdetergent but most carbonates were limited to 10%. Still Flozannonionicdetergent mixtures were not as free flowing as the invented products.Also because carbonate tends to precipitate out calcium and magnesiumand other alkaline earth metal and heavy metal ions as insolublecompounds it may give rise to chalkiness in washed materials. Still,when employed in the relatively small percentages of this invention in aspray dried product with synthetic zeolite of the type described,although both components may be considered as separately tending toincrease residue problems on washed fabrics, it is found that whenemployed in the proportions described and with hydrous sodium silicateand nonionic detergent being post-added thereto the residue level is notobjectionable. In other words, when the zeolite and carbonate are spraydried together in the proportions described, the product, which includestwo materials, each of which may develop residue problems, is found tobe better than would be expected with respect to residue deposition.Furthermore, the relatively small quantity of carbonate present reducesthe toxicity of the product and diminishes the likelihood of esophagealburns if the product should be accidentally ingested by infants orchildren.

In manufacturing the absorbent, yet comparatively high bulk densityspray dried detergent base beads, the spray drying operation isconducted in a normal manner, with only zeolite, carbonate, water andtemperature stable adjuvants, such as fluorescent brightener andpigment, normally being present. It is possible to spray dry a limitedquantity of silicate, usually no more than 15% thereof, e.g., 5 to 12%,together with the rest of the crutcher mix but generally it is preferredto post-add hydrous sodium silicate instead. If silicate is spray driedwith the rest of the base composition it will preferably be a sodiumsilicate of Na₂ O:SiO₂ ratio in the range of 1:2.0 to 1:2.5, e.g., about1:2.4.

Whether or not the silicate is present in the crutcher mix such mix willnormally include about 40 to 75% of solids and about 25 to 60% of water.Preferably, the water content will be about 25 to 50 or 60%, with thebalance of the mix being non-surface active solids. The crutcher willusually be provided with heat exchange means so that the temperature ofthe mix may be regulated, normally within the range from roomtemperature to 90° C., preferably 20° to 70° C. and most preferablyabout 45° to 65° C. Crutching times are usually in the range of 5minutes to one hour, preferably 10 minutes to 30 minutes and within thisrange will desirably be as short as possible with the obtaining of goodmixing. If any silicate is present in the crutcher mix it will usuallybe added as an aqueous solution with the other components, thecarbonate, heat-stable adjuvants and zeolite, with the zeolitepreferably being admixed last, often as a slurry (some of the water ofthe crutcher mix being utilized to form the slurry). If the silicateshould thicken the mix objectionably during crutching it may besubjected to high shear, as described in an application of the presentinventors entitled High Bulk Density Particulate Heavy Duty LaundryDetergent, executed and filed on the same dates as the presentapplication.

After completion of crutching the crutcher mix is atomized, preferablyby being forced through a circular nozzle of internal diameter in therange of about 0.5 to 2 mm., at a pressure of about 10 to 50 kg./sq. cm.gauge, into a spray tower, preferably a countercurrent spray tower, inwhich the drying air is at a temperature of about 150° to 350° C. Thetower may be about 8 to 15 meters high and about 2 to 4 meters indiameter and the product exiting therefrom is of particle sizessubstantially in the 6 to 160 U.S. Sieve Series range and is screened soas to be substantially all within such range or a narrower range, e.g.,8 to 100. Instead of high pressure atomization of the particles throughan orifice, spinning disc atomization or equivalent methods may beemployed.

After production of base particles, when they contain no silicate aparticulate solid silicate such as hydrous sodium silicate, preferablyof the type sold by Philadelphia Quartz Company as Britesil, of 1:2 or1:2.4 Na₂ O:SiO₂ ratio, is mixed with the base beads in an inclined drumor other mixing and/or tumbling device, normally over a period of about1 to 5 minutes, and nonionic detergent, in liquid state and at atemperature in the range of 20° to 70° C., preferably 30° to 60° C., issprayed onto the tumbling surfaces of the base beads, preferably afterdry mixing thereof with powdered hydrous sodium silicate. The atomizedglobules of nonionic detergent may be of any suitable size but normallyare in the 0.5 to 3 mm. diameter range, preferably 1 to 2 mm. dia. Sprayapplication of the nonionic detergent to the tumbling particles normallytakes place over a period of from 1 to 20 minutes, preferably from 2 to10 minutes. While the base particles may be heated to temperatures from30° to 60° C. to promote maintenance of normally pasty or solid nonionicdetergent in liquid form this is usually not done because heating of thedetergent suffices to accomplish this and for the normally liquiddetergents no heating is needed. After completion of addition of thenonionic detergent other materials to be post-added, such as proteolyticenzyme and perfume, may be applied. It is possible to apply theproteolytic enzyme and any other powders first, merely by mixing it orthem with the base particles including nonionic detergent, normally overa period of 1 to 10 minutes, preferably from 1 to 5 minutes, and topost-add the perfume over similar periods of time, preferably as aspray, with the sprayed globules being of sizes like those described forthe nonionic detergent. Particle sizes of the product may be regulatedby controlling the mixing conditions and the particle sizes of thepowders and sprayed droplets but usually screening after manufacturewill also be employed to obtain the desired 6 to 160 or 8 to 100 sievesize ranges.

The advantages of the present invention with respect to product andprocess have been mentioned but now will be discussed in further detail.The free-flowing high bulk density particulate product lends itself toready and convenient use. The package employed may be a "bottle", ratherthan a large detergent box, which is decidedly less convenient. Thebottle may be capped and so may be positively sealed from externalmoisture, which sometimes causes lumping of detergents, and may beprotected from spilling. Because of the higher bulk density, in additionto the packaging being of more convenient size and type, the volume ofdetergent composition to be utilized is smaller and more readilymeasured. Of course, great savings in storage and display space at pointof sale are made. Although in some circumstances a limited proportion ofphosphate, e.g., up to 10%, may be intentionally added to the presentcompositions, preferably in the crutcher mix, it is a feature of thisinvention that excellent absorption of nonionic detergent and excellentdetergency, with little or no depositing of residue onto washed items,is obtained without the use of any phosphate. Phosphates have generallybeen considered to be better builders than the other known detergentbuilders and are usually more sorptive of nonionic detergents and otherliquids. Still, in the present case, the combination of zeolite andrelatively small quantity of cabonate behaves similarly and isespecially useful in conjunction with nonionic detergent, preferablywith hydrous sodium silicate being post-added to the base beads before(but sometimes after, too) addition of nonionic detergent. The basebeads made, without any detergent or surface active agent being presentin them, are of the desired characteristics for their subsequentmanufacture into a finished detergent composition by post-spraying of anonionic organic detergent onto them. The relatively small quantity ofcarbonate keeps the alkalinity of the product low and maintains the pH,at a normal use concentration of 0.05 to 0.1% in wash water, e.g.,0.07%, (1/4 cup in a standard 17 gallon washing machine tubful of water)in the range of about 8.5 to 11, preferably 9 to 10.5. The mentioned pHis safer for washing than higher pH's and is ideal for the action of anyenzyme contained in the product and thereby helps to improve the washingand stain removing effects of the detergent composition.

The product resulting, of the composition described and made by themethods mentioned, is of excellent flow characteristics and is of ahigher density than a comparable product including bicarbonate,described in the co-filed application previously mentioned. Such may beattributable to the higher percentage of zeolite present but it issurprising that a product so high in zeolite content, with additionalsodium carbonate, should not produce unacceptably high residue depositson washed laundry. Also, in the present compositions, although it hasbeen taught that appreciable contents of silicates, whether post-addedor co-spray dried with other portions of detergent composition, arelikely to produce zeolite-silicate or other residues on washed laundry,in the present instance it is found that any residues resulting aregenerally commerically acceptable and are not cause for rejection of theproduct by the consumers.

The various advantages of the product and process are obtainable withoutextra materials or processing expenses other than the cost of themolecular sieve zeolite component and the use of phosphate is avoided.Also, because the detergent employed is nonionic it is less susceptibleto interference from water hardness ions and other impurities andtherefore the products are better washing agents under a wider varietyof conditions, including cold water washing. Even in high hardnesswaters the compositions tend to disperse better any insoluble carbonateswhich may be formed. Finally, although carbonate in waste wash waterentering the sewer and passing into inland waters is a source of carbon,required by living organisms, it is not nearly as likely to causeeutrophication of inland waters as is phosphate, in most circumstances,and accordingly, is more likely to be tolerated therein.

The following examples illustrate but do not limit the invention. Unlessotherwise indicated all parts are by weight and all temperatures are in°C.

EXAMPLE 1

    ______________________________________                                                                Percent                                               ______________________________________                                        *Neodol 23-6.5 (Shell Chemical Company                                                                  20.0                                                **Molecular Sieve Zeolite 4A, crystalline                                                               45.0                                                ultimate particle size of 4 to 8 microns                                      (Union Carbide Corp.)                                                         Na.sub.2 CO.sub.3         13.0                                                **Hydrous sodium silicate, Britesil, manufactured                                                       8.1                                                 by Philadelphia Quartz Company (Na.sub.2 O:SiO.sub.2 =                        1:2.4)                                                                        Tinopal 5BM fluorescent brightener                                                                      2.0                                                 Proteolytic enzyme        1.5                                                 Ultramarine Blue pigment  0.2                                                 Perfume                   0.3                                                 Water (including water of hydration of                                                                  9.9                                                 zeolite, silicate, etc.)                                                                                100.0                                               ______________________________________                                         *Condensation product of higher fatty alcohol of an average of 12 to 13       carbon atoms with about 6.5 mols of ethylene oxide/mol.                       **Anhydrous basis                                                        

A free flowing, high bulk density particulate detergent composition isprepared of the above formula and is of essentially globular particles,99% of which are of sizes (usually considered as of diameters) in therange of 8 to 100 mesh, U.S. Sieve Series. The product has a bulkdensity of 0.79 g./ml. and flows at a rate about 91% of that of dry sandof similar particle size, the standard for comparison. It is anexcellent heavy duty synthetic organic detergent, useful for both hotand cold water washing of both synthetic and natural fiber textiles andit does not leave objectionable residues on such textiles, such as mayoften be observed after washing with other synthetic detergentcompositions wherein substantial proportions of zeolite insolubleinorganic builder and silicate are employed together, when employed atconcentrations of 0.05 to 0.15%, e.g., 0.07%, in wash water of mediumhardness, e.g., 75 to 125 p.p.m., as CaCO₃.

The product is made by admixing in a synthetic detergent or soapcrutcher at a temperature of 60° C. (the water is initially heated andheat on the crutcher is maintained to reach and hold such temperature)zeolite and sodium carbonate, plus stable adjuvants, such as pigment andbrightener. The parts by weight employed are 55 of the zeolite(hydrated), equal to 45 parts of anhydrous zeolite, 13 of sodiumcarbonate, 0.2 of the pigment, 2 of the brightener and 50 of deionizedwater (plus 10 parts water in the zeolite). Alternatively, city water oflow hardness, less than 50 p.p.m., as calcium carbonate, is substitutedfor the deionized water in some cases. After about 20 minutes ofcrutching at a temperature of about 60° C. the crutcher mix is spraydried in a conventional countercurrent spray tower, which is about tenmeters high and three meters in diameter, by pumping it at a pressure ofabout 25 kg./sq. cm. gauge through an orifice about 1 mm. in diameterinto drying air (at a temperature of about 300° C. inlet and 110° C.outlet) so as to produce a product of a moisture content of about 14%(removable at 105° C. for 5 minutes), substantially, usually over 80%,in the 6 to 160 U.S. Sieve Series range, which product is cooled toabout room temperature (if above that) and screened so as to besubstantially all (over 99%) within such range. Alternatively, screeningis effected to particle sizes in the narrower 8 to 100 mesh range. Inboth instances the base detergent composition beads made are of a highbulk density, about 0.6 g./ml. and are free flowing, with such flowbeing about 80% or more of that of comparably sized dry sand.

With the base beads are blended about 10 parts of hydrous sodiumsilicate (8:1 parts of anhydrous silicate) of particle sizes in the 10to 100 mesh range (to result in the formula quantity of silicate in theproduct) and after about five minutes mixing there are sprayed onto themixture 20 parts of the Neodol 23-6.5 in liquid state at a temperatureof about 35° C. The particles onto which the Neodol 23-6.5 is sprayed asa liquid mist, with droplet diameters of about 2 mm., are initially atroom temperature (about 25° C.) The spraying is effected within a periodof about 8 minutes, after which the product is perfumed by spraying andthe proteolytic enzyme powder, of a particle size between 60 and 100mesh, is dusted onto the surfaces of the particles, still in the mixingdrum, each of which procedures takes about three minutes. The product isthen allowed to cool to 30° C. (if at a higher temperature) to preventloss of perfume components by evaporation.

The finished product, screened to 8 to 100 mesh size, is of the desiredhigh bulk density and very good flow characteristics and is "bottled",packed and warehoused so as to be ready for shipment. When tested, it isfound to be a satisfactory heavy duty detergent, useful for washing inboth hot and cold waters, especially so at low concentrations, e.g.,0.07% in wash water, and surprisingly, leaves little or no visibleresidue of zeolite and/or silicate or other materials on the washedfabrics. The product remains free flowing during storage. It does notcake objectionably nor does it develop lazy flow characteristics. The pHof a 0.15% solution thereof in wash water is about 9.8 and that of a0.07% solution is about 9.5, ideal pH's for proteolytic enzymaticaction, which assists the detergent composition in cleaning and removingstains from washed fabrics, whether of synthetic (nylon, polyester andpermanent press natural-synthetic blends) or natural fabrics (cottons).

When the silicate is included in the crutcher mix instead of beingpost-added (a 40% solids content aqueous solution of Na₂ O:SiO₂ ratio ofabout 1:2.4 is used instead of particulate hydrous silicate) anadditional five minutes crutching time is taken to blend the silicatewith the rest of the crutcher mix (it is added to the carbonate andwater before addition of the zeolite and the water content of thesilicate solution is taken into account in computing the amount of waterto be added to the crutcher). The product obtained is a good heavy dutydetergent of high bulk density and is sufficiently free flowing to becommercially acceptable but is not considered to be as good as theproduct of the previous example given.

In another variation of the experiment the hydrous sodium silicate, inpowder form, is admixed with the rest of the product and at leastpartially adhered to it after spraying onto such product of the nonionicdetergent. The composition obtained, while acceptable, is not as good asthat wherein the particulate hydrous sodium silicate is mixed with thezeolite first, prior to spraying onto the mix of the nonionic detergent.Flow properties are not as good, some caking on storage is noted andsome segregation occurs.

Instead of employing the inclined drum for mixing and sprayapplications, when this is replaced by a twin-shell, V- orPatterson-Kelly-type blender equivalent products are made.

Although, as indicated in the earlier portion of this example, it ispreferred to post-add the nonionic detergent to the beads shortly aftermanufacture and also to post-add any other components of the product notin the spray dried base beads this can also be done after aging of thebase beads for periods from 20 minutes to several days, without loss oftheir absorbing powers. In such cases it may be desirable to heat thebeads before application of the nonionic detergent but by proper choiceof nonionic detergent type, with respect to melting point, this isavoidable.

EXAMPLE 2

When in the processes and products of Example 1 the crystalline zeolite4 A is replaced by the corresponding amorphous material, which has anultimate particle size (diameter) in the 0.01 to 0.05 micron range orwhen the "hole" in the zeolite is increased or decreased, while stillbeing good for trapping hardness ions, e.g., to 3 to 6 Å, thecomposition obtained is of essentially the same flow and bulk densityproperties as that of the product of Example 1, is an excellent heavyduty laundry detergent which leaves no residue on washed clothing andsometimes is of even superior properties with respect to flow andabsence of residue, compared to the crystalline product. This is alsotrue but to a lesser extent when 50:50 amorphous:crystalline zeolitemixtures are employed. When type X zeolites are employed instead of typeA such effects are also obtainable. Similary, when type Y zeolites areutilized and other equivalents thereto, useful products are obtainablealthough they are not as good as those including the type A and/or Xzeolites.

The products of this example and of Example 1 are also useful when thesilicate is included partially in the crutcher and partially in theinclined drum mixer, e.g., half in each, preferably with the first beingNa₂ O:SiO₂ of 1:2.4 silicate and the latter being hydrous sodiumsilicate of 1:2 ratio. Alternatively, although not preferably, thesilicate and adjuvants may be omitted.

In addition to varying the type of zeolite present the types ofsilicates and nonionic detergent may be changed, as may be those of thevarious adjuvants. Thus, in the experiment of Example 1, instead ofemploying the hydrous silicate of Na₂ O:SiO₂ ratio of 1:2, such ratiomay be 1:1.8 or 1:2.2 and the products obtained are still like thosepreviously described. Instead of utilizing Neodol 23-6.5, Neodol 25-7and Neodol 45-11 and equally proportioned 2- and 3-component mixtures ofsuch materials are employed. Instead of Tinopal 5BM, others of thepreviously mentioned fluorescent brighteners may be substituted or thebrightener may be omitted entirely. In the latter case the productobtained is of essentially the same detersive and physical properties,although desirable brightening of laundry is noticeably diminished inthe absence of the fluorescent compound. In other variations of theprocedure and products of Example 1 the proteolytic enzyme and theUltramarine Blue are omitted from the formula. Alternatively, thecolorant is employed in larger proportion to color some productparticles while others are uncolored and beads of both types are mixedto produce a speckled version.

In addition to the various components listed others are also included,e.g., inert filler, such as sodium sulfate, anti-redeposition agents,such as sodium carboxymethyl cellulose, antibacterial agents, such astetrabromosalicylanilide, laundry sweetening (and building salts), suchas borax and bleaching materials, such as sodium perborate. The stablematerials are usually preferably added in the crutcher whereas theothers are post-added, either before or after spray-on of the nonionicdetergent. When such materials are present in the describedcompositions, for example, 5% of borax, 5% of sodium sulfate, 0.5% ofsodium carboxymethyl cellulose, 0.1% of antibacterial compound and 10%of sodium perborate, the product formula will be modified accordingly,preferably by proportional diminutions of zeolite, carbonate andsilicate contents.

In place of the sodium salts of the various mentioned componentscorresponding potassium or other suitable soluble salts, preferablyalkali metal salts, are substituted, either in whole or in part,providing that the characteristics of the products obtained areacceptable and within the ranges given.

EXAMPLE 3

A crutcher formula is made by admixing 47 parts of sodium aluminumsilicate (molecular sieve type LMS-9611, obtained from Union CarbideCorp.), 9.5 parts of light soda ash, 1.7 parts of Tinopal 5BM Conc., 0.2part of Ultramarine Blue pigment and 41.6 parts of water so that thecrutcher mix is of 48% solids content. The zeolite measurement given isthe weight of hydrated zeolite added (otherwise in this specificationand in the claims anhydrous weights are used). Wet and dry remix arealso added (q.s.) in such proportions as to maintain the 48% solidscontent. The crutcher mix is dried as described in Example 1 and a yieldof 56.4 parts results, with a moisture loss of 43.6 parts. 67.1 Parts ofproduct are mixed with 10.0 parts of Britesil H-20 (hydrous sodiumsilicate, on an "as is" basis) and 0.3 part of sodium carboxymethylcellulose (90% active) and 20.0 parts of Neodol 23-6.5 are sprayed ontothe moving mixture, in the manner described in Example 1, after whichthe product is perfumed and 1.5 parts of alkaline protease are dustedonto it. The proteolytic enzyme and sodium CMC are of the particle sizespreviously described for the enzyme and the Britesil H-20 is of thesieve analysis previously given. The nonionic detergent is at 35° C. andthe beads onto which it is sprayed are at room temperature (25° C.). Theproduct resulting contains 44.1% (anhydrous basis) of the zeolite, 11.3%of sodium carbonate, 2% of Tinopal 5BM Conc., 0.2% of Ultramarine Blue,1.5% of proteolytic enzyme, 20.0% of the nonionic detergent, 8.1% ofsilicate solids, 1.0% of sodium CMC active ingredient, 0.3% of perfumeand 11.5% of moisture (including moisture in the zeolite and hydroussodium silicate). The cup weight is 185 grams per 240 ml. andflowability is greater than 70% of that of similarly sized sand. As withthe products of the previous examples, it is a good heavy duty laundrydetergent which does not leave white deposits on washed laundry to anobjectionable extent.

EXAMPLE 4

    ______________________________________                                                               Percent                                                ______________________________________                                        Neodol 23-6.5            19.2                                                 Type 4A zeolite (hydrated, but anhyd. basis)                                                           45.2                                                 Na.sub.2 CO.sub.3        12.8                                                 Hydrous sodium silicate (anhydrous basis)                                                              8.6                                                  Fluorescent brightener   2.0                                                  Proteolytic enzyme       1.3                                                  Pigment                  0.2                                                  Moisture                 10.7                                                                          100.0                                                ______________________________________                                    

The above product is made by the method previously described forExamples 1-3. The product resulting has a cup weight of 182 g. and aflow which corresponds to 91% of that of similarly sized sand. Theparticle sizes are like those of the products previously mentioned. Itis a useful detergent and is superior to a commercially successfuldetergent when tested for cleaning power against mixed soils on aplurality of fabrics. After washing soiled laundry with it none to lightresidue is observable on dark colored clothing to a careful observer andsuch is considered to be commercially acceptable. The product ages welland passes various other tests for non-caking, appearance, stainremoval, etc.

EXAMPLE 5

The compositions of the products of the previous examples are varied±10%, ±20% and ±30%, within the ranges given and similarly, theprocedures are varied with respect to times and temperatures. Theproducts made are within the desired ranges for flow characteristics,bulk density and particle size and are of satisfactory heavy dutylaundry detersive properties. For example, the moisture content of thefinished product is varied to 5%, 6% and 10% and all of the products areof acceptable flow characteristics. The nonionic detergent content isincreased to as much as 25% with various formulas within the inventionand the silicate content is increased to 15% and, with proper selectionof the formula to produce the most free flowing product, to as high as20% and even, sometimes, 25%. Of course, in all such instances whereinthe formulas are varied, both with respect to components and withrespect to proportions, care will be taken by one of skill in the art soas to make a product of desired properties by means of a commerciallypracticable method.

The invention has been described with respect to illustrative examplesand descriptions thereof but is not to be limited to these because it isevident that one of skill in the art, with the present specificationbefore him, will be able to utilize substitutes and equivalents and makevarious modifications within the scope of the invention.

What is claimed is:
 1. A free flowing, phosphate-free, particulate,heavy duty laundry detergent product having a bulk density of greaterthan about 0.6 g per ml comprising porous, spray-dried base beads ofabout 45% crystalline zeolite particles having ultimate particle sizesof 15 microns or less, about 13% sodium carbonate, about 8% anhydroussodium silicate having an Na₂ O:SiO₂ ratio of about 1:2.4, said sodiumsilicate being combined in a hydrous form, and said beads having about20% nonionic surfactant absorbed into the interior of said beads, saidpercentages being by weight relative to the total weight of thecomposition;said nonionic surfactant containing beads being produced by:(a) preparing a crutcher mix by adding about 55 parts hydratedcrystalline zeolite particles (45 parts anhydrous basis) in the form ofan aqueous slurry to an aqueous slurry of 13 parts sodium carbonate and10 parts water-soluble sodium silicate having an Na₂ O:SiO₂ ratio of1:2.4 to form a gel, said zeolite having an average ultimate particlediameter of about 15 microns or less, the total water content of the mixbeing 50 parts and the sodium silicate being added as a 40% solidsaqueous solution; (b) shearing the gel to reduce the viscosity thereof,(c) spray-drying the crutcher mix to form said spray-dried beads havinga water content of about 14% and (d) mixing with about 80 parts of saidbeads about 20 parts of said surfactant in liquid form so that thesurfactant is absorbed into the beads to produce said nonionic detergentcontaining spray-dried beads.
 2. A detergent product according to claim1 wherein the nonionic surfactant is a condensation product of a higherfatty alcohol of an average of 12 to 13 carbon atoms with about 6.5 molsof ethylene oxide per mol of alcohol.
 3. A detergent product accordingto claim 1 wherein the zeolite particles are 4 A molecular sieves.
 4. Adetergent product according to claim 1 wherein the density is about 0.8g per ml.
 5. A detergent product according to claim 1 wherein the stepof spray drying is accomplished in drying air at an inlet temperature of300° C. and an outlet temperature of 110° C.
 6. A detergent productaccording to claim 1 wherein said zeolite particles have sizes of fromabout 4 to about 8 microns.
 7. A detergent product according to claim 1wherein the spray-dried bead particles have mesh sizes from 6 to 160 inU.S. Sieve Series.